WO2005116767A1 - ポジ型感光性組成物 - Google Patents
ポジ型感光性組成物 Download PDFInfo
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- WO2005116767A1 WO2005116767A1 PCT/JP2004/007274 JP2004007274W WO2005116767A1 WO 2005116767 A1 WO2005116767 A1 WO 2005116767A1 JP 2004007274 W JP2004007274 W JP 2004007274W WO 2005116767 A1 WO2005116767 A1 WO 2005116767A1
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- Prior art keywords
- resin
- photosensitive composition
- positive photosensitive
- formula
- development
- Prior art date
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Classifications
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41M—PRINTING, DUPLICATING, MARKING, OR COPYING PROCESSES; COLOUR PRINTING
- B41M5/00—Duplicating or marking methods; Sheet materials for use therein
- B41M5/26—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used
- B41M5/36—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties
- B41M5/368—Thermography ; Marking by high energetic means, e.g. laser otherwise than by burning, and characterised by the material used using a polymeric layer, which may be particulate and which is deformed or structurally changed with modification of its' properties, e.g. of its' optical hydrophobic-hydrophilic, solubility or permeability properties involving the creation of a soluble/insoluble or hydrophilic/hydrophobic permeability pattern; Peel development
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C1/00—Forme preparation
- B41C1/10—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme
- B41C1/1008—Forme preparation for lithographic printing; Master sheets for transferring a lithographic image to the forme by removal or destruction of lithographic material on the lithographic support, e.g. by laser or spark ablation; by the use of materials rendered soluble or insoluble by heat exposure, e.g. by heat produced from a light to heat transforming system; by on-the-press exposure or on-the-press development, e.g. by the fountain of photolithographic materials
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/02—Positive working, i.e. the exposed (imaged) areas are removed
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/06—Developable by an alkaline solution
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/22—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by organic non-macromolecular additives, e.g. dyes, UV-absorbers, plasticisers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/24—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions involving carbon-to-carbon unsaturated bonds, e.g. acrylics, vinyl polymers
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B41—PRINTING; LINING MACHINES; TYPEWRITERS; STAMPS
- B41C—PROCESSES FOR THE MANUFACTURE OR REPRODUCTION OF PRINTING SURFACES
- B41C2210/00—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation
- B41C2210/26—Preparation or type or constituents of the imaging layers, in relation to lithographic printing forme preparation characterised by a macromolecular compound or binder obtained by reactions not involving carbon-to-carbon unsaturated bonds
- B41C2210/262—Phenolic condensation polymers, e.g. novolacs, resols
Definitions
- the present invention relates to an alkali-soluble positive type photosensitive material having an infrared wavelength region laser sensitivity in which the sensitive portion becomes soluble in an alkaline developer in response to exposure to a laser beam having a wavelength of 700-1, 100 nm.
- the present invention relates to an acidic composition.
- the positive photosensitive composition of the present invention is used particularly in the field of photo applications such as printing plates, electronic parts, and precision instrument parts.
- the positive photosensitive composition forming the coating film of the lithographic printing plate described in each of the above patent documents is composed of a substance that absorbs infrared light such as an infrared absorbing dye and converts it into heat. And alkali-soluble resin such as novolak resin as the main components of the photosensitive layer, and the heat generated by exposure to infrared laser light cuts the main chain or side chain of the molecule to further increase the alkali solubility. In addition to causing a conformational change that results in a low molecular weight, a partial change causes a physical change such as a conformational change of the abrasion resin to increase the solubility in a developing solution.
- a photosensitive film is applied and formed on a copper sulfate plating surface of a plate making roll, an image is baked by a laser, developed with a laser, etched, and the resist is peeled off to remove a chrome plating. That is, a so-called etching method is performed.
- a negative photosensitive film is applied to a plate making roll, and the applied film is dried at room temperature to form a negative photosensitive film, which is baked by an argon ion laser.
- the beam diameter of the argon ion laser beam and the beam diameter of the 700-1 lOOnm laser beam are the same size, the laser resolution of the positive type is higher than that of the negative type. And the processing time can be greatly reduced.
- printing a positive image on a photosensitive film of a positive-type photosensitive composition with a laser in the infrared wavelength region is more likely to cut the pattern than printing a negative image on the photosensitive film of a negative-type photosensitive composition with an argon ion laser. Good. This is considered to be due to the difference in the pattern cut due to the difference in the composition between the positive photosensitive composition and the negative photosensitive composition.
- the high-power semiconductor laser head of CreoScitex of Canada emits a laser in the infrared wavelength range, and is mounted on an offset printing press to irradiate a positive photosensitive composition. It is a good development that can be obtained and practically used worldwide.
- a positive type photosensitive composition comprising a novolak resin and a cyanine dye was prepared, and the positive type solution was diluted with a solvent to obtain a positive type photosensitive composition.
- a sensitizer is applied to the copper sulfate plating surface of the gravure plate roll, and a laser in the infrared wavelength range is irradiated with an exposure device equipped with a high-power semiconductor laser head manufactured by CreoScitex (Sink's Laboratory Co., Ltd.).
- CreoScitex Silicon's Laboratory Co., Ltd.
- the positive photosensitive composition containing the novolak resin and the cyanine dye prepared above was applied to a plate-making roll, and barging was performed for 30 minutes so that the film surface temperature was 60 ° C. Exposure and development resulted in poor development. As a result of repeating the test many times, it was found that if the total solvent residual concentration of MEK, IPA, PM, etc. at the time of film formation was about 6% or more, the image could not be printed by the laser.
- a positive photosensitive composition in order to reduce the residual solvent concentration to 6% or less, preferably to 3% or less, and to provide necessary and sufficient adhesion.
- a silane coupling agent is added as an adhesive to increase the adhesive force of the photosensitive film.
- exposure and development can be performed slightly better. It became so. Specifically, for example, a 200 mm thick plate-making roll is rotated at a low speed of 25 rpm to apply a positive photosensitive agent, and continues to rotate to prevent dripping, allowing it to dry naturally.
- the residual solvent concentration is less than 2%.
- the image could be printed with a laser and developed.
- the adhesion to the film is not the best, and the exposure and development are slightly better. I did not cross.
- the film surface temperature is set to 130 ° C, it takes more than 100 minutes for burung and subsequent cooling, requires a large amount of heat energy, increases running costs, and is not practical. I understand.
- the film surface temperature is set to 130 ° C., the hydrogen bond of the alkali-soluble organic polymer having a phenolic hydroxyl group is strengthened to make development difficult, and the sensitivity is lowered due to denaturation of the cyanine dye.
- Gravure plate rolls include those having a roll base material made of aluminum and those made of iron.
- the wall thicknesses are all different.
- the heater is heated for the same time, the heat is transferred to the roll substrate, and the film surface temperature is not always heated to 130 ° C. It was considered important to lower the temperature and eliminate the problem of specific heat capacity.
- imidazole which is a curing accelerator, was used as an adhesive instead of the silane coupling agent.
- silane coupling agent there was no particular difference from the case of the silane coupling agent. It was the same as for the drug.
- an alkali-soluble organic polymer material having a phenolic hydroxyl group and a stock solution of a positive-type photosensitive composition comprising a photothermal conversion material, which absorbs infrared light from an image exposure light source and converts it into heat are used.
- a test was conducted to form and develop a photosensitive film on a copper sulfate plating roll at room temperature 25 ° C, adding and replacing various adhesives, and found that the photosensitive film of a positive photosensitive composition containing a titanium organic compound was added. Tsu, Te was able to significantly reduce the Bayungu temperature (see Patent Document 10.) 0
- the film of the positive photosensitive composition to which the titanium organic compound was added the film could be formed well even at a vari-ng temperature of 46 ° C, the sensitivity was improved, and the development was easy. Only However, in the test in which the burning treatment was not performed, good film formation could not be performed, resulting in poor development.
- baljung temperature can be reduced to around 50 ° C
- the need for baljung means that cooling must be performed after baljung, and time and energy are required for baljung and subsequent cooling. This is disadvantageous because it requires a lot of effort and the equipment line is lengthened by the length of the Bering equipment, which increases equipment and running costs. Burning also causes thinning of the resist during development and causes pinholes. Therefore, there is a strong demand for the development of a positive photosensitive film that does not require burning.
- the present inventor has made the development theme that practical use of a positive type photosensitive film is not necessary!
- the adherence of the positive type photosensitive film itself by adding a bonding agent without depending on the verjung is considered.
- the diffusivity decreases as the surface dries as time passes.
- the applied film no longer drips, it is considered that the residual solvent can be effectively reduced by forcibly applying a negative pressure to the film surface to diffuse the residual solvent into the air. Then, after the coating film stopped dripping, the plate-making roll was rotated at a high speed, and it was found that the residual solvent concentration could be reduced to 3% or less in a short time.
- the solvent concentration can be reduced to 6% in a very short time without performing verging.
- the plate-making roll is horizontally supported at both ends by a spiral scan type coating device and rotated at the required low speed, and the photosensitive agent flows out from the upper end.
- the pipe is moved to one end and the other end of the plate-making roll so that the gap is not opened by the spiral scan method, and the photosensitive agent is spouted by an amount necessary for coating.
- the test photosensitive liquid is applied evenly so that the overlap is negligible, and then the rotation is continued to set the photosensitive film with a dry degree with the solvent vaporized so that no dripping occurs.
- the plate is transferred to a laser exposure device, etc., and the plate-making roll is rotated at a required high speed for a required time to rub against the air.
- the residual solvent in the photosensitive layer to establish a technique for obtaining the formation of the low concentration of residual solvents which image printing properties by a laser to diffuse released into the air can be expressed.
- the photosensitive liquid is uniformly applied to a 200 mm test roll, the rotation is stopped at 25 rpm for 5 minutes, and the rotation is stopped. After waiting for 5 minutes, the dripping is observed and visually observed. After confirming that no dripping occurred, the test roll was stopped by rotating it at 100 rpm for 20 minutes, and the residual solvent concentration in the photosensitive film was measured to be 2.3%.
- an undiluted solution of a positive-type photosensitive composition comprising an alkali-soluble organic polymer having a phenolic hydroxyl group and a photothermal conversion material that absorbs infrared light from an image exposure light source and converts it into heat
- a bad organic treatment results in poor development. And development were excellent, and the best resist pattern was obtained.
- Patent Document 1 JP-A-10-268512
- Patent Document 2 JP-A-11 194504
- Patent Document 3 JP-A-11 223936
- Patent Document 4 JP-A-11-84657
- Patent Document 5 JP-A-11-174681
- Patent Document 6 JP-A-11-231515
- Patent Document 7 International Publication No. 97Z39894
- Patent Document 8 International Publication No. 98Z42507
- Patent Document 9 JP-A-2002-189294
- Patent Document 10 Japanese Patent Application Laid-Open No. 2004-133025
- Patent Document 11 Japanese Patent Publication No. 47-25470
- Patent Document 12 Japanese Patent Publication No. 48-85679
- Patent Document 13 Japanese Patent Publication No. 51-21572
- adhesion aids include butylpyrrolidone z-butyl acetate copolymer, bulpyrrolidone z-dimethylaminoethyl methacrylate copolymer, vinylpyrrolidone z-vinyl alcohol.
- the present invention relates to a positive photosensitive composition in which the sensitive portion becomes soluble in an alkaline developer in response to exposure to laser light having a wavelength of 700-1, 100 nm, and the humidity in a coating work chamber is 25%.
- the humidity in a coating work chamber is 25%.
- the object of the present invention is to provide a positive-type photosensitive composition excellent in latitude in image printing and development by laser.
- the positive photosensitive composition of the present invention comprises an alkali-soluble organic polymer substance (A) having a phenolic hydroxyl group, and absorbs infrared light from an image exposure light source to heat.
- Photothermal conversion substance to be converted (B), (1) vinylpyrrolidone Z vinyl acetate copolymer, (2) butylpyrrolidone / dimethylaminoethyl methacrylate copolymer, (3) butylpyrrolidone Z butyl force prolatamtam Z dimethylaminoethyl methacrylate copolymer, (4) Polyacetic acid Bull, (5) Polybutyl butyral, (6) Polybutylformal, (7) Styrene Z maleic acid copolymer, (8) Terpene phenol resin, (9) Alkyl phenol resin, (10) Melamine It is characterized by containing at least one resin (C) selected from the group consisting of Z-formaldehyde resin and (11) ketone resin, and a dissolution inhibitor (D).
- C At least one resin selected from the group consisting of Z-formaldehyde resin and (11) ketone resin
- D dissolution inhibitor
- the dissolution inhibitor (D) is preferably a compound represented by the following chemical formula (1).
- the photothermal conversion substance (B) is a compound represented by the following general formula (2).
- R 1 to R ° each independently represent a hydrogen atom, an alkyl group having 13 to 13 carbon atoms, or an alkoxy group having 13 to 13 carbon atoms
- X is a halogen atom, CIO
- the photothermal conversion substance (B) is preferably a compound represented by the following general formula (3). [0040] [Formula 3]
- each of R 7 —R 1Q independently represents a hydrogen atom, a methoxy group, N (CH 3), or N (CH 3
- the photo application technology of the present invention is characterized by using the positive photosensitive composition of the present invention.
- Examples of the photo application include printing plates, electronic components, and precision device components.
- the plate making method of the present invention is characterized by using the positive photosensitive composition of the present invention.
- printing plates such as intaglio (gravure), planographic, letterpress, and stencils can be prepared.
- a general plate making process of a gravure plate using the positive photosensitive composition of the present invention as a photosensitive solution is as follows.
- a general plate-making process for a lithographic plate (PS plate) using the positive photosensitive composition of the present invention as a photosensitive solution is as follows.
- CTP PS plate
- Exposure light source: semiconductor laser 830nm, 220mj / cm 2
- Development ⁇ 4. Printing.
- the positive photosensitive composition of the present invention is an alkali-soluble positive photosensitive composition having a laser sensitivity in an infrared wavelength region in which the sensitive portion becomes soluble in a developer in response to exposure to laser light in an infrared wavelength region.
- the composition has an excellent effect as described below.
- the resist image has a gloss with little film loss, and even if it is corroded as it is, pinholes do not occur and gravure plate making can be performed.
- a resist image having printing durability enough to print several thousand sheets or more for printing or the like can be obtained, and pinholes can be avoided during handling after development of the photosensitive film before development, or scratch resistance is reduced. improves.
- FIG. 1 is a drawing showing a photosensitive liquid test pattern and measurement points used in Example 1, (a) is a test pattern, and (b) is an enlarged view of a circle portion of (a). .
- the positive photosensitive composition of the present invention is characterized by containing the following components (A) to (D).
- Examples of the alkali-soluble organic polymer substance (A) having a phenolic hydroxyl group include novolak resin, resole resin, polyvinyl phenol resin, and an acrylic acid derivative having a phenolic hydroxyl group.
- epoxy resins having a phenolic hydroxyl group e.g., epoxy Z phenolic.
- novolak resin, resole resin, or polyvinyl phenol resin as disclosed in Patent Document 6, etc. Fat is preferred! / ⁇ .
- These alkali-soluble organic polymer substances (A) may be used alone or in combination of two or more.
- the novolak resin is a resin obtained by polycondensing at least one kind of phenols with at least one kind of aldehydes or ketones under an acidic catalyst
- the resole resin is a novolak resin. Is a resin polycondensed in the same manner except that an alkali catalyst is used in place of the acid catalyst in the polycondensation of In novolak and resole resins, phenol, o-talesol, m-cresol, p-cresol, 2,5-xylenol, 3,5-xylenol, Polycondensates of solcinol or mixed phenols thereof with formaldehyde, acetoaldehyde or propionaldehyde are preferred.
- the novolak resin and the resol resin preferably have a weight average molecular weight (MW) of 1,500 to 150,000 in terms of polystyrene measured by gel permeation chromatography.
- Examples of the polybutylphenol resin include a resin obtained by polymerizing one or more hydroxystyrenes in the presence of a radical polymerization initiator or a cationic polymerization initiator. Hydroxystyrene polymers having a C.sub.14 alkyl group as a substituent on a benzene ring and unsubstituted benzene ring hydroxystyrene polymers are preferred.
- a polybutylphenol derivative for example, a derivative of polybutylphenol with t-butylation or styrenation, etc.
- a copolymer of bürphenol with another bule-based monomer for example, bulephenol-methyl methacrylate copolymer
- Polymers, a phenol-styrene copolymer, a phenol-2-hydroxyethyl methacrylate copolymer, a phenol-maleimide copolymer, and the like may be used.
- the content ratio of the alkali-soluble organic polymer substance (A) in the positive photosensitive composition of the present invention is not particularly limited, but the components (A), (B), (C), and (D)
- the amount is preferably from 80 to 95% by weight, more preferably from 90 to 94% by weight, based on the total solid content of the component.
- the photothermal conversion substance (B) is not particularly limited as long as it is a compound capable of converting absorbed light into heat, but the absorption band is partially or wholly in the infrared region at a wavelength of 700-1, 100 nm.
- a light-absorbing dye which does not substantially respond to absorption or a compound represented by the following general formula (2) or (3) or a derivative thereof is particularly preferable.
- R 1 to R 6 each independently represent a hydrogen atom, an alkyl group having 13 to 13 carbon atoms, or an alkoxy group having 13 to 13 carbon atoms.
- X— is a counter ion, X is a halogen atom, C lO
- R 7 — R 1Q each independently represent a hydrogen atom, a methoxy group, N (CH 3) 2, or N (C
- Y— is an anion
- Y is C H— B (C H)
- a near-infrared absorbing dye represented by the following chemical formulas (4) and (7) having a maximum absorption wavelength in a near-infrared region is more preferable.
- the so-called cyanine dyes in a broad sense, which are bound, are typical examples. Specific examples include quinoline dyes (so-called cyanine dyes), indole dyes (so-called indocyanine dyes), and benzothiazole dyes (so-called dyes).
- Thiocyanine type iminocyclohexadiene type (so-called polymethine type), pyrylium type, thiapyrylium type, squarylium type, croconium type, azurenium type and the like.
- quinoline type, indole type, benzothiazole type, iminocyclohexyl type Sagen, pyrylium or thiapyrylium are preferred.
- phthalocyanine cyanine is preferred.
- the photothermal conversion material (B) has an absorption band in a part or the whole of an infrared wavelength region having a wavelength of 700-1, 100 nm and absorbs laser light in the infrared wavelength region to thermally decompose. It has properties and participates in alkali-soluble depolymerization and abrasion by thermal cutting of molecules of the alkali-soluble organic polymer substance having a phenolic hydroxyl group.
- the amount of the light-to-heat conversion material added is related to the excess or shortage of heat generated by exposure, and the intensity of the infrared laser light depends on the thermal decomposition of the alkali-soluble organic polymer substance present in the exposed portion. It is set to an appropriate amount because it is related to the excess and shortage.
- the content ratio of the photothermal conversion substance (B) in the positive photosensitive composition of the present invention is 0.1% based on the total solid content of the components (A), (B), (C) and (D). It is preferably 1 to 10% by weight, more preferably 1 to 4% by weight.
- the resin (C) includes (1) butylpyrrolidone Z butyl acetate copolymer, (2) butylpyrrolidone Z dimethylaminoethyl methacrylate copolymer, and (3) butylpyrrolidone Z bulcap. Mouth ratatam Z-dimethylaminoethyl methacrylate copolymer, (4) polybutyl acetate, (5) polybutyral, (6) polybutylformal, (7) styrene Z maleic resin, (8) terpene phenol resin, (9) Alkyl phenol resin; (10) Melamine formaldehyde resin; and (11) Ketone resin. At least one alkali-soluble resin selected from the group and functions as an adhesion improver.
- the (1) butylpyrrolidone Z butyl acetate copolymer (hereinafter referred to as PVPZVA copolymer) is a thermoplastic resin obtained by copolymerizing vinylpyrrolidone and butyl acetate, and has the following general formula (8) ).
- n and m are each an integer of 1 or more.
- the ratio of butylpyrrolidone to butyl acetate in the PVPZVA copolymer is not particularly limited, but a ratio of vinylpyrrolidone to butyl acetate of 70Z30 to 30Z70 is preferred, and 50Z50 is more preferred.
- the method for producing the PVPZVA copolymer is not particularly limited, but a linear random copolymer obtained by subjecting vinylpyrrolidone and vinyl acetate to free radical polymerization is preferred.
- the molecular weight of the PV PZVA copolymer is also not particularly limited, but is preferably 10,000 to 60,000 force, and more preferably 20 to 50,000 force! / ⁇ .
- the (2) bulletpyrrolidone Z dimethylaminoethyl methacrylate copolymer has a structure represented by the following general formula (9).
- n and m are each an integer of 1 or more.
- the (3) bulletpyrrolidone Z-bilcaprolatatam Z-dimethylaminoethyl methacrylate copolymer is a copolymer of bulletpyrrolidone, bullet-prolatatam and dimethylethyl methacrylate, represented by the following general formula (10) It has the structure shown.
- n, m, and 1 are each an integer of 1 or more.
- the (4) polyvinyl acetate is a homopolymer of vinyl acetate or a copolymer containing vinyl acetate as a main component, and has a structure represented by the following general formula (11).
- n is an integer of 1 or more.
- the polyvinyl acetate for example, Sakunol SN-09T (trade name) manufactured by Denki Kagaku Kogyo Co., Ltd. is preferably used.
- PVB polybutylbutyral
- n, m and 1 are each an integer of 1 or more.
- Specific examples of polyvinyl butyral are products of Denki Kagaku Kogyo Co., Ltd., Denka Butyral 5000A and 6000EP, Products of Sekisui Chemical Co., Ltd., low polymerization type BL-1, BL-2, BL-2, BL-S, BX-L, medium polymerization type BM-1, BM-2, BM-5, Suitable examples include BM-S, high polymerization type BH-3, BH-S, BX-1, BX-2, BX-5, BX-55, etc., which are soluble in various solvents. The use of BL-S, BM-S, BH-S is particularly preferred.
- PVFM polyvinyl formal
- n, m, and 1 are each an integer of 1 or more.
- the method for producing polyvinyl formal is not particularly limited.For example, polyvinyl acetate is dissolved in acetic acid, formaldehyde and sulfuric acid are added, and the Kennig reaction and the formal Ligation reaction are performed simultaneously, and dilute sulfuric acid is added to the reaction mixture. Polyvinylformal is precipitated, and the product is obtained through solvent recovery, washing, and drying steps.
- the (7) styrene Z maleic acid resin is a copolymer obtained by copolymerizing a styrene monomer and a maleic acid monomer, a derivative of the copolymer, or a modification thereof. Is a thing.
- the (7) styrene Z maleic acid-based resin preferably contains a carboxyl group so that the acid value is 30 to 200, particularly 50 to 170. A weight average molecular weight of 1,500-100,000 is suitable.
- the styrene monomer is styrene or a derivative thereof, for example, styrene, ex-methylstyrene, m or p-methoxystyrene, p-methylstyrene, p-hydroxystyrene, and 3-hydroxymethyl-4-.
- Preferred examples include hydroxy-styrene.
- the maleic acid monomer is maleic acid or a derivative thereof, and is maleic anhydride, maleic acid, monomethyl maleate, monoethyl maleate, mono-n-propyl maleate, monoisopropyl maleate, Maleic esters such as mono-n-butyl maleate, monoisobutyl maleate and mono-tert-butyl maleate are preferred.
- the (7) styrene Z maleic acid-based resin is a copolymer of a styrene monomer having a structure represented by the following general formula (14) and a maleic acid monomer [hereinafter, It is referred to as copolymer (a). ].
- vinyl monomers such as acrylic monomers (for example, alkyl methacrylates such as methyl methacrylate and t-butyl methacrylate, and alkyl acrylates) are further added. Those copolymerized can also be used.
- R u represents a hydrogen atom or a methyl group
- R 13 is shows a hydrogen atom or a hydroxyalkyl radical
- R 14 and R 15 each independently represent a hydrogen atom, a lower alkyl group or a group having a reactive double bond
- m and n are each an integer of 1 or more, and preferably m ⁇ n.
- styrene Z maleic acid-based resin a copolymer obtained by modifying the copolymer (a) with a compound having a reactive double bond [hereinafter, referred to as a copolymer (b)] . ] May be used.
- the copolymer (b) can be produced by reacting a compound having a reactive double bond with an acid anhydride group or a carboxy group in the copolymer (a). it can. In this case, it is preferable that a carboxyl group remains in the copolymer in order to improve adhesion.
- the compound having a reactive double bond is preferably a compound having a carbon-carbon double bond.
- unsaturated alcohols for example, aryl alcohol, 2-butene 12- Alcohol, furfuryl alcohol, oleyl alcohol, cinnamyl alcohol, 2-hydroxyethyl atalylate, hydroxyethyl metharylate, N-methylol atalylamide, etc.
- alkyl (meth) acrylate eg, methyl meta Tarylate, t-butyl metharylate, etc.
- Compounds e.g., glycidyl Atari rate, glycidyl methacrylate Tari rate, ⁇ Li glycidyl ether, alpha - E tilde glycidyl Atari rate, crotonyl glycidyl ether, Itakon Sanmo-alkyl monoglycidyl ester
- the method for producing the copolymers (a) and (b) is not particularly limited, and can be carried out according to a known method (for example, see Patent Documents 11 to 13).
- the provision of a reactive double bond to the copolymer is preferred from the viewpoint of the degree of curing and printing durability.
- terpene phenol resin (8) conventionally known terpene phenol resins can be widely used.
- Tamanor 803L and 901 (trade names manufactured by Arakawa Chemical Industry Co., Ltd.) are mentioned as preferable examples.
- Tamanor 520S, 521, 526, 586 and 572S are preferred examples.
- the (10) melamine formaldehyde resin is a resin obtained by an addition condensation reaction of melamine and formaldehyde, and known melamine formaldehyde resins can be widely used. Specifically, for example, it is preferable to use Vanceline SM-960 (trade name) manufactured by Rima Kasei Co., Ltd.
- the ketone resin (11) may be a known ketone resin, and is not particularly limited. For example, it can be obtained by reacting a ketone with formaldehyde by a known method. Ketones include, for example, methyl ethyl ketone, methyl isobutyl ketone, acetophenone, cyclohexanone, methylcyclohexanone, etc., and cyclohexanone and acetophenone are particularly preferred.
- a cyclohexanone-based ketone resin represented by the following formula (15) and an acetophenone-based ketone resin having a structure represented by the following formula (16) are preferable.
- [0101] [Formula 17]
- n are each an integer of 1 or more.
- the content of the resin (C) in the positive photosensitive composition of the present invention is based on the total solid content of the components (A), (B), (C) and (D). It is preferably 1 to 40% by weight, more preferably 5 to 30% by weight.
- the dissolution inhibitor (D) is blended for the purpose of increasing the time difference in solubility between the exposed part and the unexposed part in an alkali developing solution, and forms a hydrogen bond with the alkali-soluble organic polymer.
- those which have a function of reducing the solubility of the polymer substance hardly absorb light in the infrared region, and are not decomposed by light in the infrared region are used.
- dissolution inhibitor (D) a known dissolution inhibitor can also be used. Specifically, sulfonic esters, phosphoric esters, aromatic carboxylic esters, aromatic disulfones, carboxylic anhydrides, aromatic ketones, aromatic aldehydes, aromatic amines, aromatic ethers, etc., ratatone skeleton, Acid-coloring dyes having a thiolatatatone skeleton, an N, N-diarylamide skeleton, or a diarylmethylimino skeleton, base coloring dyes having a latatatone skeleton, a thiolatatatone skeleton, or a sulfora exoskeleton, a nonionic surfactant, and the like. Among these, acid-coloring dyes having a rataton skeleton are preferred.
- the content of the dissolution inhibitor (D) is determined based on the component (A),
- the amount is preferably 0.5 to 8% by weight, more preferably 115% by weight, based on the total solid content of the components (B), (C) and (D). These dissolution inhibitors may be used alone or in combination of two or more.
- the poly-type photosensitive composition of the present invention may further contain, if necessary, various colorants such as pigments or dyes, sensitizers, development accelerators, coatability improvers, and the like. Additives may be added.
- the sensitizer a compound that generates an acid by light (photoacid generator) is preferable.
- the development accelerator for example, it is preferable to add a small amount of a dicarboxylic acid or an amine or a glycol.
- the positive photosensitive composition of the present invention is usually used as a solution dissolved in a solvent.
- the ratio of the solvent to be used is usually in the range of about 110 to 20 times by weight based on the total solid content of the photosensitive composition.
- Solvents that have sufficient solubility for the components used and give good coating properties As long as it is not limited, cellosolve solvents, propylene glycol solvents, ester solvents, alcohol solvents, ketone solvents, and highly polar solvents can be used.
- cellosolve-based solvent include methyl sorb, ethyl sorb, methyl sorb acetate, ethyl sorb acetate and the like.
- propylene glycol solvents examples include propylene glycol monomethyl enoate ether, propylene glycol monoethyl enoate ether, propylene glycol monoole butyl ether, propylene glycol monomethino oleate acetate, propylene glycol oleco Monoethynoleate enorea acetate, propylene glycol monobutyl ether acetate, dipropylene glycol dimethyl ether and the like can be mentioned.
- ester solvents examples include butyl acetate, amyl acetate, ethyl butyrate, butyl butyrate, ethyloloxalate, ethyl ethyl pyruvate, ethyl 2-hydroxybutyrate, ethyl ethyl acetate, methyl lactate, ethyl ethyl lactate, and 3-methoxypropionate. Acid methyl and the like.
- alcohol solvents include heptanol, hexanol, diacetone alcohol, furfuryl alcohol and the like.
- the highly polar solvent examples include ketone solvents such as cyclohexanone and methyl amyl ketone such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
- ketone solvents such as cyclohexanone and methyl amyl ketone such as dimethylformamide, dimethylacetamide, and N-methylpyrrolidone.
- acetic acid, a mixed solvent thereof, and those obtained by adding an aromatic hydrocarbon to them, and the like can be mentioned.
- the positive photosensitive composition of the present invention is usually prepared by dissolving each of the above-mentioned components in a solvent such as a cellosolve-based solvent or a propylene glycol-based solvent. After applying to the copper plating surface or copper sulfate plating surface and air-drying, it is rotated at high speed to cut off the wind on the surface of the plate making roll, and the mass action due to centrifugal force in the photosensitive film and a slight negative pressure near the surface By reducing the residual solvent concentration to 6% or less by the above method, a positive photosensitive film having a photosensitive composition layer formed on the surface of the support is obtained.
- a solvent such as a cellosolve-based solvent or a propylene glycol-based solvent.
- the thickness of the coating film is preferably in the range of 16 / zm, more preferably 3-5 ⁇ m.
- a light source for imagewise exposing the positive photosensitive composition layer a semiconductor laser or a YAG laser that generates an infrared laser beam having a wavelength of 700 to 100 nm is preferable.
- Le A solid laser such as a bee laser and an LED can be used.
- the light strength of the laser light source 2. It is particularly preferred to OX 10 6 mjZs'cm 2 or more and it is preferable to implement 1. OX 10 / s -cm 2 or more.
- an inorganic alkali for example, a salt of Na or K
- an organic alkali for example, TMAH
- Developers that also have an inorganic or organic alkaline strength, such as Tetra Methyl Ammonium Hydroxide) or choline, are preferred.
- Development is usually performed by immersion development, spray development, brush development, or ultrasonic development.
- a positive photosensitive composition (solid content: 5%) was prepared using the compounding substances and compounding ratios shown in Table 1, and used as a test photosensitive liquid.
- Novolak resin PR— NMD— 100 (Sumitomo Bakelite)
- Light absorbing dye 1 cyanine dye PVPZVA copolymer: copolymer of burpyrrolidone and butyl acetate (bulpyrrolidone Z butyl acetate) with a molecular weight of 46,000 and a glass transition point of 96 ° C (50/50)
- Dissolution inhibitor 1 manufactured by Honshu Chemical Industry Co., Ltd., trade name: TrisP-PA (compound represented by the above formula (1))
- the following experiment was performed using the obtained test photosensitive solution.
- the experiment was performed in a laboratory at 25 ° C and the humidity conditions shown in Table 2.
- a 200 mm-diameter plate-making roll, whose base material is iron, copper sulfate plated and mirror polished, is transferred to a fountain coating device (a device equipped with a dehumidifier and caro-humidifier to control the humidity as desired). Both ends were chucked, rotated at 25 rpm, and thoroughly wiped with a wiping cloth.
- the fountain coating device is intended to prevent the solvent in the positive-type photosensitive composition from evaporating during the coating and changing the proportion of the solvent.
- test photosensitive liquid is discharged at the upper end force is positioned so as to have a gap of about 500 m at one end of the plate making roll, and the test photosensitive liquid is spouted in an amount necessary for coating. Then, the test roll was moved evenly at a rate of 25 rpm for 5 minutes from the end of the application by moving the pipe one end force of the plate-making roll to the other end to apply the test photosensitive solution uniformly by a snoral scan method.
- test roll was rotated at 100 rpm for 20 minutes and stopped, and the residual solvent concentration in the photosensitive film was measured to be 2.9%.
- test roll was mounted on an exposure apparatus (manufactured by Synch Laboratories, Inc.) equipped with a high power semiconductor laser head manufactured by Cleotex, and the test roll was irradiated with a laser in the infrared wavelength range to be positive.
- the image is printed, and then the test roll is attached to the developing device and rotated to raise the developing tank and develop until no residue remains. It was.
- the developer used was KOH 4.2% (25 ° C).
- the obtained resist image was evaluated with a microscope. Table 2 shows the results.
- the measurement was performed using a cell storage device (a device capable of automatically measuring the halftone dot opening ratio) manufactured by Dai Nippon Printing Co., Ltd.
- tesa test DIN EN ISO 2409 The cross-cut adhesion test using a tesa tape was evaluated as ⁇ when 100 squares were all left, ⁇ when peeled in less than 20% range, and X when peeled 20% or more.
- Exposure is determined and sensitivity is determined based on the reproducibility of the image pattern.
- the exposure machine used was a Thermore imaging head from Creo.
- the film thickness before development and the film thickness after development were measured using a FILMETRICS Thin Film Analyzer F20 (manufactured by Filmetrics Co), which is a device for measuring the thickness of the coating film, and the residual film ratio was calculated.
- FIG. 1 shows the photosensitive liquid test pattern and measurement points.
- Table 3 shows the check items and measurement methods for the measurement points in Fig. 1.
- the positive photosensitive composition of Example 1 had a room temperature of 25 ° C. and a humidity of 35—55.
- Example 4 The experiment was carried out in the same manner as in Example 1 except that the component (B) in the composition was changed as shown in Table 4. The measurement was performed at a humidity of 45%. Table 4 shows the results.
- the compounding amount of the component (B) is the same as in Example 1, and the dye 2 to the dye 6 are the compounds represented by the above formulas (2), (4) to (7), respectively. .
- Example 5 The experiment was performed in the same manner as in Example 1 except that the component (A) in the composition was changed as shown in Table 5. The measurement was performed at a humidity of 45%. Table 5 shows the results.
- the compounding amount of the component (A) is the same as in Example 1, and the resins 2 to 4 are as follows.
- Resin 1 Alkyl phenol Resin (trade name: HITANOL 2181, Hitachi Chemical Co., Ltd.)
- Resin 2 p-Bufenphenol butyl acrylate copolymer (trade name Marukarinka-CB A, manufactured by Maruzen Oil Co., Ltd.)
- Resin 3 Polyvinylphenol Resin (trade name Marcarinka I-M, manufactured by Maruzen Oil Co., Ltd.) [0139] (Examples 10-20)
- Polymer 1 GAFQUAT 734 (Bulpyrrolidone Z dimethylaminoethyl methacrylate copolymer manufactured by ISP)
- Polymer 2 G AFFIX VC-713 (Vinyl pyrrolidone / vinyl caprolactam / dimethylaminoethyl methacrylate terpolymer manufactured by ISP)
- Polymer 3 Sakunol SN-09T (manufactured by Denki Kagaku Kogyo Co., Ltd., polyacetate biel)
- Polymer 4 Denkabutyral # 3000 (Denka Butyral Co., Ltd., polyvinyl butyral)
- Polymer 5 Berek K type (manufactured by Chisso, polyvinyl formal)
- Polymer 6 Oxylac SH-101 derivative (Styrene with glycidyl methacrylate added)
- Polymer 7 Tamanol 803L (Arakawa Chemical Industries, Ltd., terpene phenol resin)
- Polymer 8 Tamanol 520S (Arakawa Chemical Industries, Ltd., alkyl phenol resin)
- Polymer 9 Nonserine SM-960 (Harima Chemical Co., Ltd.) Co., Ltd., melamine formaldehyde resin)
- Polymer 10 No, Ilac 111 (Cyclohexane resin, manufactured by Hitachi Chemical Co., Ltd.)
- Polymer 11 Hilac 110H (Acetohphenone resin manufactured by Kadatsu Kasei Co., Ltd.)
- Example 7 The experiment was carried out in the same manner as in Example 1 except that the components (A) and (C) used the resins and polymers shown in Table 7 or Table 8. The measurement was performed under the condition of a humidity of 45%. The results are shown in Tables 7 and 8. In Tables 7 and 8, the amounts of component (A) and component (C) were the same as in Example 1, resins 2 and 3 were the same as in Table 5, and polymers 1 and 11 were as shown in Table 5. Same as 6.
- Example 1 The experiment was carried out in the same manner as in Example 1 except that the composition of the positive photosensitive composition was changed as shown in Table 9. The measurement was performed at a humidity of 45%. Table of results
- novolak resin, light absorbing dye 1 and solvent are the same as those in Table 1, and the other components are as described below.
- Titanium organic compounds Organix TA-10 (titanium alkoxide) manufactured by Matsumoto Kogyo Seiyaku Co., Ltd.
- Imidazole silane a silane coupling agent having a structure represented by the following formula (17).
- R 1 to R 4 are each an alkyl group, and n is an integer of 13 to 13.
- Comparative Example 3 ⁇ 180-250 60 0-XX [0150] As shown in Table 10, in all of Comparative Examples 13 to 13, the image disappeared after development, and no development latitude was obtained.
- the positive photosensitive composition of the present invention is preferably used for forming a positive photosensitive film on the copper sulfate plating surface of a plate roll for gravure printing, but is not limited thereto.
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- Physics & Mathematics (AREA)
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- Materials For Photolithography (AREA)
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
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PCT/JP2004/007274 WO2005116767A1 (ja) | 2004-05-27 | 2004-05-27 | ポジ型感光性組成物 |
DE602004015513T DE602004015513D1 (de) | 2004-05-27 | 2004-05-27 | Positive lichtempfindliche zusammensetzung |
EP04745380A EP1750175B1 (en) | 2004-05-27 | 2004-05-27 | Positive photosensitive composition |
JP2005511741A JP4081491B2 (ja) | 2004-05-27 | 2004-05-27 | ポジ型感光性組成物 |
US10/596,741 US20070154835A1 (en) | 2004-05-27 | 2004-05-27 | Positive photosensitive composition |
CN200480001742.0A CN1791837A (zh) | 2004-05-27 | 2004-05-27 | 正型感光性组合物 |
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PCT/JP2004/007274 WO2005116767A1 (ja) | 2004-05-27 | 2004-05-27 | ポジ型感光性組成物 |
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US (1) | US20070154835A1 (ja) |
EP (1) | EP1750175B1 (ja) |
JP (1) | JP4081491B2 (ja) |
CN (1) | CN1791837A (ja) |
DE (1) | DE602004015513D1 (ja) |
WO (1) | WO2005116767A1 (ja) |
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KR101400193B1 (ko) * | 2010-12-10 | 2014-05-28 | 제일모직 주식회사 | 컬러필터용 감광성 수지 조성물 및 이를 이용한 컬러필터 |
CN106933037B (zh) * | 2017-04-12 | 2020-06-26 | 安徽强邦印刷材料有限公司 | 一种热敏阳图ctp版感光组合物的制备方法 |
CN113406863B (zh) * | 2021-06-16 | 2023-06-06 | 田菱智能科技(昆山)有限公司 | 一种光-热双固化感光胶、其制法及使用方法 |
Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11506550A (ja) * | 1996-04-23 | 1999-06-08 | ホーセル・グラフィック・インダストリーズ・リミテッド | 感熱性組成物および該組成物を使用したリソグラフィックプリンティングフォームの作製方法 |
JPH11202481A (ja) * | 1997-10-28 | 1999-07-30 | Mitsubishi Chemical Corp | ポジ型感光性組成物、ポジ型感光性平版印刷版及びその処理方法 |
JP2001133965A (ja) * | 1998-11-16 | 2001-05-18 | Mitsubishi Chemicals Corp | ポジ型感光性平版印刷版、その製造方法およびポジ画像形成方法 |
JP2002023364A (ja) * | 2000-07-13 | 2002-01-23 | Mitsubishi Chemicals Corp | ポジ型感光性組成物及びポジ型感光性平版印刷版 |
JP2002189294A (ja) * | 2000-12-21 | 2002-07-05 | Mitsubishi Chemicals Corp | ポジ型画像形成材料 |
JP2003122025A (ja) * | 2001-10-15 | 2003-04-25 | Fuji Photo Film Co Ltd | ポジ型感光性平版印刷版の作製方法 |
JP2003345016A (ja) * | 2002-05-23 | 2003-12-03 | Fuji Photo Film Co Ltd | 樹脂組成物 |
JP2003345017A (ja) * | 2002-05-23 | 2003-12-03 | Fuji Photo Film Co Ltd | 樹脂組成物 |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE3040157A1 (de) * | 1980-10-24 | 1982-06-03 | Hoechst Ag, 6000 Frankfurt | Lichtemopfindliches gemisch und damit hergestelltes lichtempfindliches kopiermaterial |
DE3582697D1 (de) * | 1984-06-07 | 1991-06-06 | Hoechst Ag | Positiv arbeitende strahlungsempfindliche beschichtungsloesung. |
TW304235B (ja) * | 1992-04-29 | 1997-05-01 | Ocg Microelectronic Materials | |
DE69810242T2 (de) * | 1997-10-28 | 2003-10-30 | Mitsubishi Chemical Corp., Tokio/Tokyo | Positiv arbeitendes strahlungsempfindliches Gemisch, positiv arbeitende lichtempfindliche Flachdruckplatte und Verfahren zur Bebilderung der Druckplatte |
US6475693B1 (en) * | 1998-12-10 | 2002-11-05 | Clariant Finance (Bvi) Limited | Positively photosensitive resin composition |
US6635724B2 (en) * | 2001-07-31 | 2003-10-21 | Ppg Industries Ohio, Inc. | Modified aminoplast crosslinkers and powder coating compositions containing such crosslinkers |
JP3844069B2 (ja) * | 2002-07-04 | 2006-11-08 | 信越化学工業株式会社 | レジスト材料及びパターン形成方法 |
US6911300B2 (en) * | 2003-11-10 | 2005-06-28 | Think Laboratory Co., Ltd. | Photogravure plate making method |
US7226724B2 (en) * | 2003-11-10 | 2007-06-05 | Think Laboratory Co., Ltd. | Positive-type photosensitive composition |
-
2004
- 2004-05-27 DE DE602004015513T patent/DE602004015513D1/de not_active Expired - Lifetime
- 2004-05-27 US US10/596,741 patent/US20070154835A1/en not_active Abandoned
- 2004-05-27 WO PCT/JP2004/007274 patent/WO2005116767A1/ja active IP Right Grant
- 2004-05-27 EP EP04745380A patent/EP1750175B1/en not_active Expired - Lifetime
- 2004-05-27 CN CN200480001742.0A patent/CN1791837A/zh active Pending
- 2004-05-27 JP JP2005511741A patent/JP4081491B2/ja not_active Expired - Lifetime
Patent Citations (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH11506550A (ja) * | 1996-04-23 | 1999-06-08 | ホーセル・グラフィック・インダストリーズ・リミテッド | 感熱性組成物および該組成物を使用したリソグラフィックプリンティングフォームの作製方法 |
JPH11202481A (ja) * | 1997-10-28 | 1999-07-30 | Mitsubishi Chemical Corp | ポジ型感光性組成物、ポジ型感光性平版印刷版及びその処理方法 |
JP2001133965A (ja) * | 1998-11-16 | 2001-05-18 | Mitsubishi Chemicals Corp | ポジ型感光性平版印刷版、その製造方法およびポジ画像形成方法 |
JP2002023364A (ja) * | 2000-07-13 | 2002-01-23 | Mitsubishi Chemicals Corp | ポジ型感光性組成物及びポジ型感光性平版印刷版 |
JP2002189294A (ja) * | 2000-12-21 | 2002-07-05 | Mitsubishi Chemicals Corp | ポジ型画像形成材料 |
JP2003122025A (ja) * | 2001-10-15 | 2003-04-25 | Fuji Photo Film Co Ltd | ポジ型感光性平版印刷版の作製方法 |
JP2003345016A (ja) * | 2002-05-23 | 2003-12-03 | Fuji Photo Film Co Ltd | 樹脂組成物 |
JP2003345017A (ja) * | 2002-05-23 | 2003-12-03 | Fuji Photo Film Co Ltd | 樹脂組成物 |
Non-Patent Citations (1)
Title |
---|
See also references of EP1750175A4 * |
Also Published As
Publication number | Publication date |
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DE602004015513D1 (de) | 2008-09-11 |
EP1750175B1 (en) | 2008-07-30 |
CN1791837A (zh) | 2006-06-21 |
EP1750175A4 (en) | 2007-06-27 |
US20070154835A1 (en) | 2007-07-05 |
JPWO2005116767A1 (ja) | 2008-04-03 |
EP1750175A1 (en) | 2007-02-07 |
JP4081491B2 (ja) | 2008-04-23 |
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